Method and composition containing nitroparaphenylene dyes for dyeing keratinic fibers

ABSTRACT

COMPOSITION CONTAINING NITROPARAPHENYLENE DIAMINE DERIVATIVES FOR DYEING KERATINIC FIBERS AND METHOD OF APPLYING SAID COMPOSITION TO THE HAIR, WHEREIN SAID DIAMINE DERIVATIVES HAVE THE FORMULA:   1-(R-NH-),2-(O2N-),4-(R-N(-Z)-)BENZENE   IN WHICH:   R REPRESENTS H OR A LOWER ALKYL; Z REPRESENTS H, AN   1-R&#39;&#39;,4-(SO2-)BENZENE   RADICAL IN WHICH R&#39;&#39; REPRESENTS H, METHYL, OR NO2, OR AN OC-R&#34; RADICAL IN WHICH R&#34; REPRESENTS A LOWER ALKYL; AND AT LEAST ONE OF R AND Z IS H; R1 REPRESENTS A LOWER ALKYL, LOWER HYDROXYALKYL, LOWER ALKOXYALKYL OR   -(CH2)N-N(-R2)-R3   IN WHICH N IS A WHOLE NUMBER BETWEEN TWO AND SIX INCLUSIVE, WHILE R2 AND R3 REPRESENT H, A LOWER ALKYL, OR A LOWER HYDROXY ALKYL, AND THE ALKYL PORTION OF R, R&#34;, R1, R2 AND R4 HAVING 1 TO 6 CARBON ATOMS.

United States Patent The portion of the term 6: the patent subsequent to Nov. 2, 1988, has been disclaimed Int. Cl. A61k 7/12; D06p 3/02 US. Cl. 8-10 Claims ABSTRACT OF THE DISCLOSURE Composition containing nitroparaphenylene diamine derivatives for dyeing keratinic fibers and method of applying said composition to the hair, wherein said diamine derivatives have the formula:

NHR;

in which:

R represents H or a lower alkyl;

Z represents H, an

radical in which R represents H, methyl, or N0 or an OC-R" radical in which R" represents a lower alkyl; and at least one of R and Z is H;

R represents a lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl or /R2 (0 Hz) n N in which n is a whole number between two and six inclusive, while R and R represent H, a lower alkyl, or a lower hydroxy alkyl, and the alkyl portion of R, R, R R and R having 1 to 6 carbon atoms.

The present invention relates to a method of preparing compositions having the formula:

NHR1 (I) in which R represents hydrogen, or a lower alkyl radical, which may or may not be substituted, and especially a hydroxyalkyl, carboxyalkyl, carbamylalkyl or amino-alkyl radical, which may or may not be substituted on the amine function, the nitrogen of which may form part of a heterocyclic ring; and in which Z represents hydrogen, an

radical in which R represents hydrogen, methyl, or an N0 group, or an OCR" radical in which R" represents a lower alkyl, at least one of the Z and R radicals representing hydrogen; and in which R represents a lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl or in which n is a whole number between two and six inclusive and R and R may be identical or different and represent a hydrogen atom, a lower alkyl, or a lower hydroxyalkyl, while the nitrogen atom adjacent R and R may form therewith a heterocyclic ring such as a morpholino or piperidino radical; and the alkyl portion of R, R", R R and R having 1 to 6 carbon atoms and the corresponding quaternary derivatives. In this process an amine having the formula R NH in which R has the significant hereinbefore indicated, is reacted with a compound having the formula:

in which R has the significance hereinbefore indicated, X represents a halogen atom, and preferably chlorine,

and Z is an group or an OC--R", with R and R" having the significances hereinbefore indicated, after which, when it is desired to obtain a product in which Z represents hydrogen, the resulting product is subject to acid hydrolysis.

The compounds according to Formula I may be quaternized in a conventional manner, using a quaternizing agent such as methyl sulfate or an alkyl or aryl halide.

Another object of the present invention is to provide as new articles of manufacture the compounds responding to general Formula I in which:

R1="(CH2)fl N\ 3 (R and R having the significances hereinbefore assigned thereto), and R=an alkyl amino, the amine function of which may be substituted, as well as compound in which Z=H R =alkoxy alkyl, and R=H or alkyl, and compounds in which R=H,

(R' having the significance hereinbefore indicated), and

(R and R having the significances hereinbefore indicated) as well as the corresponding quaternary derivatives, when these compositions contain a tertiary amine function.

The above compositions are particularly suitable for use in dyeing keratinic fibers, and especially hair.

They have a strong affinity for fibers, good stability under exposure to light and inclement weather, and are very soluble in water.

It is consequently another object of this invention to provide a new composition for dyeing keratinic fibers, and particularly hair, essentially characterized by the fact that it contains at least one of the above-defined dyes in solution.

The dyeing compositions according to the invention are preferably simple aqueous solutions having a pH value between 4 and 10 and preferably between 7 and 10 inelusive.

These dyeing compositions may also contain various ingredients conventionally used in hair dyes, such for example, as organic solvents, thickeners, detergents, emollients, per-fumes and lacquers. The dyes according to the invention may also be mixed with each other, or with other dyes, such as nitro, azo, or anthraquinone dyes, or any other type of dye used to color hair.

These dyes may be used without employing an oxidizing agent. The time of contact with the hair may vary within broad limits, but lies preferably between and 30 minutes. The compositions according to the invention may be used at various temperatures, but are preferably applied at room temperature. The concentration of the dyes may also vary over a broad range, but is preferably selected between 0.1% and 3% by weight.

The present invention also comprises a method of dyeing hair essentially characterized by the fact that a hair dyeing composition as hereinbefore described is applied to the hair for between 5 and 30 minutes, after which the hair is washed, rinsed, and dried.

In order that the invention may be better understood, several methods of synthesizing the compositions of Formula I and using said compositions to dye hair will now be described.

EXAMPLE 1 Preparation of 1-hexylamino-2-nitro-4-amino benzene 0.1 mol (21.5 g.) of 2-nitro-4-acetylamino chlorobenzene is dissolved in 2 mols (202 g.) of hexylamine. This is heated to reflux for 8 hours. The excess aliphatic amine is driven off under vacuum. The resulting oily residue is treated with 200 cm. of a normal hydrochloric acid solution cooled to 0 C. The mixture is then dried, and washing with alcohol yields 15 g. of practically pure 1 hexylamino 2 nitro 4 amino benzene hydrochloride. This product results from the de-acetylation of part of the 1 hexylamino 2 nitro 4 acetylamino benzene formed after substitution of the chlorine atom. The hydrochloride, when treated with ammoniacal solution, forms 12.8 g. of 1 hexylamino 2 nitro 4 amino benzene which, after recrystallization in toluene, melts at 75 C. Analysis of this product yields the following results:

Calculated for Analysis CrzHmNaOz Found 0, percent. 60. 76 60. 95-60. 84

H, percent. 8. 01 8. 22-8. 19

N, percent..- 17. 72 17. 69-17. 71

EXAMPLE 2 Preparation of l-N-fl-diethylaminoethylamino-2-nitro- 4-acetylamino benzene EXAMPLE 3 Preparation of 1-N-B-diethylaminoethylamino-Z-nitro- 4-amino benzene The product prepared in Example 2 is hydrolized with hydrochloric acid to form 1 N )8 diethylaminoethylamino-2-nitro-4-amino benzene, which melts at 65 C.

EXAMPLE 4 Preparation of methyl 3 [N (2-nitro-4-acetylamino) phenyl]-aminoethyl-methyldiethylammonium sulfate 1 N )9 diethylamino 2 nitro 4 acetylamino benzene is obtained as described as in Example 2. 0.017 mols (5 g.) of this compound is dissolved in 50 cc. of chlorobenzene at 40 C. 0.019 mol (1.8 cc.) of methyl sulfate is added little by little, while stirring and the reaction mixture is kept at 40 C. for 4 hours. After cooling, drying yields 6.36 of the desired quaternary ammo nium salt, which melts at 133 C. After recrystallization in alcohol, the product, on analysis, yields the following results.

Calculated for Analysis C15H2$N40 75 Found C, percent 45. 71 45. 94-45. 89 H, percent..- 6. 67 6. 76-6. 69 N,percent 13. 33 13. 11-13. 10

EXAMPLE 5 Preparation of 1-N-,8-diethy1aminoethylamino-2-nitro-4- N'-methylamino benzene 0.011 mol (5 g.) of l-N-,B-diethylarnin0ethylamino-Z- nitro-4-(N-methyl-N benzylsulfonyl)amino benzene monohydrochloride, prepared as described in Example 10 of US. Ser. No. 728,750, filed on May 13, 1968, by Gregoire Kalopissis, Andree Bugaut and Vahan Zorayan, is added little by little, while stirring, to 30 cc. of sulfuric acid at 0 C. When this has completely dissolved, the reaction mixture is left to stand for six hours at room temperature, and then poured into 300 cc. of ice Water. Alkalization with a five times normal sodium hydroxide solution and drying yields 3.1 g. of l-N-B-diethylaminoethyl-amino-2-nitro-4 N methylamino benzene, which melts at 74 C.

EXAMPLE 6 Preparation of 1-N-B-hydroxyethylamino-2-nitro-4-N- methylamino benzene 0.028 mol (10.1 g.) of 1-N-B-hydroxyethylamino-Z- nitro-4(N-methyl-N-benzensulfonyl) amino benzene, the preparation of which has been described in Example 12 of the above-mentioned US. patent application, is dissolved in 20 cc. of concentrated hydrochloric acid which has first been brought to 95 C. This is heated for an hour in a boiling water-bath, 20 cc. of water is then added, the mixture is cooled to 10 C., and drying then yields 5.5 g. of practically pure l-N-B-hydroxyethylamino- 2-nitro-4-N'-methylamino benzene monohydrochloride. This hydrochloride, when treated with a normal sodium hydroxide solution, yields 4.5 g. of l-N-/3-hydroxyethylamino-Z-nitro-4-N-methylamino benzene which melts at 123 C.

EXAMPLE 7 First method of preparing 1-N-- -methoxypropylamino-2- nitro-4-N'-methylamino benzene hydrochloride 0.02 mol (7.58 g.) of N-y-methoxypropylamino-Z- nitro-4-(N'-methyl-N' benzenesulfonyl)amino benzene, the preparation of which has been described in the aforementioned U.S. patent application, is dissolved in 35 cm. of sulfuric acid at 0 C. The reaction mixture is left to stand for hours, poured into 500 cc. of cracked ice and alkalized with a 5 times normal sodium hydroxide solution. The desired product is then extracted by means of methylisobutylketone. After washing, the methylisobutylketone solution with water, and drying it with sodium sulfate, the solvent is evaporated under a vacuum. The oily residue is dissolved in cc. of propanol. After bubbling dry hydrochloric acid into the iced propanolic solution, drying yields 5.10 g. of l-N-y-methoxypropylamino-2-nitro-4-N'-methylamino benzene hydrochloride, which melts and decomposes between 115 and 120 C. Analysis of the product yields the following results:

Second method of preparing l- -methoxypropylamino- 2-nitro-4-methylamino benzene hydrochloride 0.0071 mol (2 g.) of 1w-methoxypropylamino-2-nitro- 4-(N-methyl-N-acetyl)-amino benzene prepared as described in Example 14 of the above-mentioned U.S. patent application, is heated for 1 hour and 30 minutes in a boiling water bath in 20 cc. of concentrated hydrochloric acid to which 40 cc. of water has been added. After cooling, the reaction mixture is diluted, alkalized with a five times normal sodium hydroxide solution, and drying yields 1.61 g. of 1-'y-methoxypropylamino-Z-nitro- 4-N-methylamino benzene, which after recrystallization in benzene, melts at 52 C. After dissolving this product in propanol and bubbling hydrochloric acid thereinto, the corresponding hydrochloride is obtained.

EXAMPLE 9 Preparation of 1-N-,B-diethylaminoethylamino-2-nitro-4- (N'-,B-diethylaminoethyl)-amino benzene 0.0387 mol (19 g.) of l-N-(ti-diethylaminoethyl)- amino-2-nitro-4-(N'-;8 diethylaminoethyl N benzene sulfonyl)-amino benzene is dissolved in 76 cc. of concentrated sulfuric acid while maintaining its temperature at 40 C. The reaction mixture is kept at this temperature for four hours and then poured into 600 cc. of ice water, after which it is alkalized with a 5 times normal sodium hydroxide solution and the desired product is then extracted with methylisobutylketone. After washing the methylisobutylketone solution and drying it on sodium sulfate, the solvent is evaporated under vacuum, thereby isolating in the form of a violet oil, 12 g. of practically pure 1 N-(B-diethylaminoethyl)amino-2-nitro-4-N'-(;3-

diethylaminoethyl)amino benzene. Analysis of this product yields the following results:

Calculated for Analysis C13H33N5O2 Found C, percent 61. 53 61. 54-61. 49

H, percent 9. 40 9. 42-9.

N, percent 19. 94 20. 10-20. 15

EXAMPLE 10 Preparation of 1-N-p-aminoethylamino-2-nitro-4- benzenesulfonyl benezene 0.1 mol (31.2 g.) of 2-nitro-4-benzenesulfonylamino Calculated for Analysis 014E150 4N4S1HC1 Found N, percent 15. 03 15. 08-15. 13 01, percent 8. 59 8. 72-8. 78

Preparation of 1N- S-aminoethylamino-2-nitro-4-aminobenzene dihydrochloride 0.1 mol (37.2 g.) of 1-N-,B-aminoethylamino-2-nitro-4- benzenesulfonylamino benzene monohydrochloride, prepared as described in Example 10 of the present application, is heated for three hours in a boiling water-bath in 500 cc. of concentrated hydrochloric acid. Cooling and drying yields 26 g. of 1-N-,B-aminoethylamino-2-nitro-4- amino benzene dihydrochloride.

EXAMPLE 12 Preparation of 1-N- -hydroxypropylamino-2-nitro-4-N'- methylamino benzene 0.0075 mol (2 g.) of 1-N-'y-hydroxypropylamino-2- nitro-4-(N-methyl-N-acetyl)amino benzene, which has been prepared as described in Example 16 of the hereinbefore mentioned U.S. patent application is heated for an hour in a boiling water-bath in 20 cc. of concentrated hydrochloric acid mixed with 40 cc. of water. After cooling this mixture is alkalized with a five times normal sodium hydroxide solution, and drying yields 1.6 g. of l-N-y-hydroxypropylamino-Z-nitro-4 N methylamino benzene which, after recrystallization in toluene, melts at 107.5 C. Analysis of this product yields the following results:

Calculated for Analysis CmHnOa a Found C, percent 53. 33 53. 37-53. 23 H, percent 6. 67 6. 65-6. 74 N, percent 18. 18. 72-18. 87

EXAMPLE 13 Preparation of 1-N-B-diethylaminoethylamino-2-nitro-4- N'-/3-hydroxyethylamino benzene dihydrochloride 0.0106 mol (5 g.) of l-N-/3-diethylaminoethylamino-Z- nitro-4-(N-;3-hydroxyethyl N' benzenesulfonyDamino benzene monohydrochloride, prepared as described in Example 17 of the hereinbefore mentioned U .S. patent application is heated for an hour in a boiling water bath in 10 cc. of concentrated hydrochloric acid. The reaction mixture is poured into cc. of ice water, alkalized with a five times normal sodium hydroxide solution, and the desired product is extracted with methylisobutylketone. After washing the methylisobutylketone solution with water and drying it on sodium sulfate the solvent is evaporated under vacuum. The oily residue is dissolved in 20 cc. of propanol. After bubbling, dry hydrochloric acid into the iced propanolic solution, drying yields 3.5 g. of 1-N-fi-diethylaminoethylamino-2-nitro-4-N' f3 hydroxy ethylamino benzene dihydrochloride which, after recrystallization in a mixture of propyl alcohol and concentrated hydrochloric acid, melts and decomposes between 178 and 7 183 C. Analysis of this product yields the following results:

Calculated for Analysis C1rH2tN OsClzz Found 0, percent 45. 52 45. 64-45. 69

H, percent 7. 04 7.11-7. 25

N, percent 15.17 15. 38-15. 23

EXAMPLE 14 The following composition is prepared:

G. 1-(N-fi-diethylaminoethyl)amino-2-nitro-4-(N'-B diethylaminoethyl)amino benzene trihydrochloride 0.4

[[sooctylphenylpolyethoxyethanol 1.5 NH OH q.s.p., pH 9. Water, q.s.p 100 When this is applied to natural light chestnut hair and left thereon for ten minutes, a grayish purple shade re- Sodium carbonate q.s.p., pH 9. Water, q.s.p 100 This composition is applied to natural light chestnut hair left thereon for 10 minutes, rinsed and shampooed. The result is a grayish purple shade.

What is claimed is:

1. A process for dyeing hair comprising applying to said hair in amounts effective to dye said hair a composition having a pH of 4-10 and comprising an aqueous solution of a dye selected from the group consisting of (1) a dye having the formula NHR; wherein R is selected from the group consisting of hydrogen, alkyl, amino-alkyl, amino-dialkyl and alkylaminodialkyl, wherein the alkyl moiety of each has 1-6 carbon atoms, Z is selected from the group consisting of hydrogen,

wherein R is selected from the group consisting of hydrogen, methyl and N0 and R" is lower alkyl with the proviso that at least one of Z and R is hydrogen,

/R2 R1 is (OH2)1J N a wherein n is an integer of 2-6 and R and R are selected from the group consisting of hydrogen, lower alkyl, lower hydroxy alkyl wherein the alkyl moiety of each has 1-6 carbon atoms, and together with the nitrogen atom to which they are attached form a radical selected from the group consisting of morpholinyl and piperidinyl (2) a quaternary derivative of the dye in (1) with a member selected from the group consisting of methyl sulfate, alkyl halide and phenyl halide and (3) the monoand di-hydrochloride of the dye in (1), said dye being present in amounts of about 0.1-3 weight percent of said composi- 8 tion, permitting said composition to remain in contact with said hair for a period of about 5-30 minutes and thereafter washing, rinsing and drying said hair.

2. A composition for dyeing keratinic fibers comprising an aqueous solution of a dye selected from the group consisting of (1) a dye having the formula wherein R is selected from the group consisting of hydrogen, methyl and N0 and R is lower alkyl with the aminodialkyl, wherein the alkyl moiety of each has 1-6 carbon atoms, Z is selected from the group consisting of hydrogen,

u -soi--n' and -o-R'( wherein R is selected from the group consisting of hydrogen, methyl and N0 and R" is lower alkyl with the proviso that at least one of Z and R is hydrogen,

R is -(oH2),,N

wherein n is an integer of 2-6 and R and R are selected from the group consisting of hydrogen, lower alkyl, lower hydroxy alkyl, wherein the alkyl moiety of each has 1-6 carbon atoms and together with the nitrogen atom to which they are attached form a radical selected from the group consisting of morpholinyl and piperidinyl, (2) a quaternary derivative of the dye in (1) with a member selected from the group consisting of methyl sulfate, alkyl halide and phenyl halide and (3) the hydrochloride of the dye in (1), said dye being present in amounts of about 0.1-3 weight percent of said composition.

3. The composition of claim 2 having a pH ranging between 4-10 inclusive.

4. The composition of claim 2 having a pH ranging between 7-10 inclusive.

5. The composition of claim 2 wherein said dye is selected from the group consisting of 1-hexylamino-2- nitro-4-amino benzene, 1-N-B-diethylaminoethylamino-Z- nitro-4-acetylamino benzene, l-N-fi-diethylaminoethylamino-2-nitro-4-amino benzene, rnethyl-fi-[N-(2-nitro-4- acetylamino)phenyl]-amino ethyl methyldiethylammonium sulfate, 1-N-B-diethylaminoethylamino-Z-nitro-4-N- methylamino benzene, l-N-B-diethylaminoethylamino-Z- nitro-4-(N'-,8-diethylaminoethyl)-aminobenzene, 1-N 8- aminoethylamino-Z-nitro-4-benzenesulfamyl benzene and 1-N-;3-aminoethylamino-2-nitro-4-amino benzene dihydrochloride.

References Cited UNITED STATES PATENTS 3,274,249 9/1966 Brunner et a1. 8-10 X FOREIGN PATENTS 758,111 5/1967 Canada 8-11 DONALD LEVY, Primary Examiner P. C. IVES, Assistant Examiner US. Cl. X.R. 

